CN105175297A - Synthesis and application of 4-formyl benzoic acid adamantine ester condensed o-aminobenzene thiophenol schiff base nickel complex - Google Patents
Synthesis and application of 4-formyl benzoic acid adamantine ester condensed o-aminobenzene thiophenol schiff base nickel complex Download PDFInfo
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- CN105175297A CN105175297A CN201510671437.2A CN201510671437A CN105175297A CN 105175297 A CN105175297 A CN 105175297A CN 201510671437 A CN201510671437 A CN 201510671437A CN 105175297 A CN105175297 A CN 105175297A
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Abstract
The invention discloses synthesis and application of a 4-formyl benzoic acid adamantine ester condensed o-aminobenzene thiophenol schiff base nickel complex. The 4-formyl benzoic acid adamantine ester condensed o-aminobenzene thiophenol schiff base nickel complex is finally synthesized by adamantanol, 4-formyl benzoic acid, o-amino thiophenol and nickel acetate which serve as raw materials, and 4-formyl benzoic acid adamantine ester and 4-formyl benzoic acid adamantine ester condensed o-aminobenzene thiophenol schiff base which serve as midbodies. The 4-formyl benzoic acid adamantine ester condensed o-aminobenzene thiophenol schiff base nickel complex is synthesized by adopting esterification reaction and condensation reaction, is higher in electrochemical activity, and can be used as an electronic medium applied to a chemical modified electrode.
Description
Technical field
The present invention relates to the synthesis of 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex, described Schiff base nickel complex has stronger electrochemical activity, can repair electroactive substance in electrode be applied at analysis field as chemistry.
Background technology
Since first the people such as Czech chemist Landa in 1932 have isolated a small amount of diamantane (0.0004%) from the petroleum cuts in Nan Molawei oil field, always in the ascendant to the research of diamantane and derivative thereof.In recent years, in fields such as medicine, polymer, tensio-active agent, photoelectric materials, relevant report about diamantane and derivative application thereof also gets more and more, and receives Chinese scholars and more and more pays close attention to, therefore have people to be called by diamantane " fine chemicals raw material of new generation ".Schiff compounds, is utilize carbonyl and amino condensation to generate, can forms the molecule of coordination and conjugated structure containing C=N double bond, has the advantages such as synthesis difficulty is little, productive rate is high, step is few, raw material is cheap.Current schiff base compounds is widely used in the fields such as catalysis, medicine and photoelectric material.The special performance that metal complexes containing π-electron conjugated system has in optical, electrical, magnetic etc. due to it, has caused extensive attention and the further investigation of people.Adamantane Schiff's base enjoys the concern of people, but preparation and the property Quality Research of diamantane ester class Schiff's base and nickel complex thereof but rarely have report.
Summary of the invention
The object of this invention is to provide a kind of 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex synthetic method and as the application of electronic media in chemically modified electrode.
The described structural formula containing 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex is:
Described 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols and nickel ion press 2:1 coordination.
Preparing the above-mentioned 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex concrete steps that contain is:
(1) synthesis of diamantane ester:
Take 4-carbamoyl benzoate 0.5g (0.0033mol), adamantanol 0.608g (0.004mol), dicyclohexylcarbodiimide (DCC) 0.858g, DMAP (DMAP) 0.067g, wherein dicyclohexylcarbodiimide (DCC), DMAP (DMAP) are as catalyzer, proceed in 100mL single port flask, half an hour is vacuumized again with oil pump, add 30mL anhydrous methylene chloride, stir 8 hours under nitrogen protection, occur white precipitate dicyclohexylurea (DCU) (DCU); Filter, get filtrate, utilize Rotary Evaporators to be spin-dried for, obtain white powder, purify obtains diamantane ester sterling to column chromatography (sorbent material is silica gel, analytical pure methylene dichloride and the analytical pure sherwood oil of eluent to be mass percent be 1:1), molecular formula is 1HNMR (500MHz, CDCl3) δ 10.10 (s, 1H), 8.19 – 8.10 (m, 2H), 7.93 (dd, J=7.4,1.2Hz, 2H), 2.27 (d, J=13.8Hz, 9H), 1.79 – 1.68 (m, 6H).Fusing point 134 DEG C ~ 136 DEG C, productive rate 40%.
(2) synthesis of 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff's base:
0.5g4-carbamoyl benzoate diamantane ester is dissolved in the dehydrated alcohol of 20mL, is slowly added drop-wise in the ethanol solution of the 10mL containing 0.19g near amino thiophenols; Dropwise, add 6-8 and drip analytical pure Glacial acetic acid, under nitrogen protection stirring at room temperature 5 hours; have a large amount of yellow mercury oxide to produce, leave standstill, cooling, filter, dehydrated alcohol recrystallization, dry; obtain pure yellow powder 4-carbamoyl benzoate diamantane ester contracting Ortho-Aminophenol Schiff's base, hydrogen spectrum is
1hNMR (500MHz, CDCl
3) δ 8.14 (d, J=13.3Hz, 1H), 7.98 (d, J=8.3Hz, 2H), 7.58 (d, J=8.3Hz, 2H), 7.06 (d, J=7.6Hz, 1H), 6.98 (dd, J=11.1,4.2Hz, 1H), 6.79 (t, J=7.5Hz, 1H), 6.71 (d, J=7.8Hz, 1H), 6.42 (s, 1H), 2.25 (d, J=12.9Hz, 9H), 1.78 – 1.67 (m, 6H).Fusing point 220 DEG C ~ 223 DEG C, productive rate 78%.
(3) synthesis of nickel complex:
0.5g4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff's base is dissolved in 35mL dehydrated alcohol and N, in dinethylformamide (DMF) mixed solvent, dehydrated alcohol and analytical pure N, (DMF volume ratio is 6:1 to dinethylformamide, under 65 DEG C of condition of heating and stirring, slowly to the 10mL ethanol solution containing 0.039g nickelous acetate in solution, reflux 3 hours, have garnet to precipitate to generate, leave standstill, cooling, filter, dehydrated alcohol recrystallization, dry, obtain 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex dark red powder.
4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex can be applied in chemically modified electrode as electronic media.
The invention provides one and utilize esterification, condensation reaction, the 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex of synthesis has higher electrochemical activity, can be applied in chemically modified electrode as electronic media.
Accompanying drawing explanation
Fig. 1 is 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex DMF solution circulated voltammogram.
Fig. 2 is the thermogravimetric curve figure of 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex.
Embodiment
Illustrate the present invention further below in conjunction with specific embodiment, but embodiment does not limit the scope of the invention.
Embodiment:
Structural formula containing 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex is:
4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex preparation method is:
(1) synthesis of diamantane ester:
Take 4-carbamoyl benzoate 0.5g (0.0033mol), adamantanol 0.608g (0.004mol), dicyclohexylcarbodiimide (DCC) 0.858g and DMAP (DMAP) 0.067g; wherein DCC, DMAP are as catalyzer; proceed in 100mL single port flask; half an hour is vacuumized again with oil pump; add 30mL anhydrous methylene chloride; stir 8 hours under nitrogen protection, occur white precipitate dicyclohexylurea (DCU) (DCU).Filter, get filtrate, utilize Rotary Evaporators to be spin-dried for, obtain white powder, purify obtains diamantane ester sterling to column chromatography (sorbent material is silica gel, analytical pure methylene dichloride and the analytical pure sherwood oil of eluent to be mass percent be 1:1), and hydrogen spectrum is 1HNMR (500MHz, CDCl3) δ 10.10 (s, 1H), 8.19 – 8.10 (m, 2H), 7.93 (dd, J=7.4,1.2Hz, 2H), 2.27 (d, J=13.8Hz, 9H), 1.79 – 1.68 (m, 6H), fusing point 134 DEG C ~ 136 DEG C, productive rate 40%.
(2) synthesis of 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff's base:
By in the dehydrated alcohol of the molten people 20mL of 0.5g4-carbamoyl benzoate diamantane ester, be slowly added drop-wise to the ethanol solution of the 10mL containing 0.19g near amino thiophenols; Dropwise, add 6-8 and drip analytical pure Glacial acetic acid, under nitrogen protection stirring at room temperature 5 hours; have a large amount of yellow mercury oxide to produce, leave standstill, cooling, filter, dehydrated alcohol recrystallization, dry; obtain pure yellow powder 4-carbamoyl benzoate diamantane ester contracting Ortho-Aminophenol Schiff's base, hydrogen spectrum is
1hNMR (500MHz, CDCl
3) δ 8.14 (d, J=13.3Hz, 1H), 7.98 (d, J=8.3Hz, 2H), 7.58 (d, J=8.3Hz, 2H), 7.06 (d, J=7.6Hz, 1H), 6.98 (dd, J=11.1,4.2Hz, 1H), 6.79 (t, J=7.5Hz, 1H), 6.71 (d, J=7.8Hz, 1H), 6.42 (s, 1H), 2.25 (d, J=12.9Hz, 9H), 1.78 – 1.67 (m, 6H).Fusing point 220 DEG C ~ 223 DEG C, productive rate 78%.
(3) synthesis of nickel complex:
0.5g4-carbamoyl benzoate diamantane ester contracting near amino thiophenols contracting near amino thiophenols Schiff's base is dissolved in 35mL dehydrated alcohol and N, in dinethylformamide (DMF) mixed solvent, dehydrated alcohol and analytical pure N, dinethylformamide (DMF) volume ratio is 6:1, under 65 DEG C of condition of heating and stirring, slowly to the 10mL ethanol solution containing 0.039g nickelous acetate in solution, reflux 3 hours, have garnet to precipitate to generate, leave standstill, cooling, filter, dehydrated alcohol recrystallization, dry, obtain 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex dark red powder.
Thermogravimetric analysis is carried out to 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex, the results are shown in Figure 2.Analysis chart 2 shows, nickel complex is before 228 DEG C, and curve is platform, illustrates that nickel complex decomposes.When temperature is more than 228 DEG C, thermogravimetric curve obviously starts to glide, and show nickel complex generation thermolysis, 430 DEG C time, TG curve occurs platform again, rate of weight loss is 82.1%, residual rate is 18.9%, and according to the general knowledge of nickel complex, residuals should be nickel oxide, calculate by part and metallic nickel ions 2:1 coordination mode, theoretical value is 8.66%, and actual result, may containing remaining carbon distribution higher than theoretical value.
4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex is applied in chemically modified electrode as electronic media.
Claims (2)
1. a preparation method for 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex, is characterized in that concrete steps:
(1) synthesis of diamantane ester
:
Take 4-carbamoyl benzoate 0.5g, adamantanol 0.608g, dicyclohexylcarbodiimide 0.858g and DMAP 0.067g, wherein dicyclohexylcarbodiimide, DMAP are as catalyzer, proceed in 100mL single port flask, half an hour is vacuumized again with oil pump, add 30mL anhydrous methylene chloride, stir 8 hours under nitrogen protection, occur white precipitate dicyclohexylurea (DCU); Filter, get filtrate, utilize Rotary Evaporators to be spin-dried for, obtain white powder, column chromatography is purified and is obtained diamantane ester sterling, and sorbent material is silica gel, analytical pure methylene dichloride and the analytical pure sherwood oil of eluent to be mass percent be 1:1, and diamantane ester hydrogen is composed and is
1hNMR (500MHz, CDCl3) δ 10.10 (s, 1H), 8.19 – 8.10 (m, 2H), 7.93 (dd, J=7.4,1.2Hz, 2H), 2.27 (d, J=13.8Hz, 9H), 1.79 – 1.68 (m, 6H), fusing point 134 DEG C ~ 136 DEG C;
(2)the synthesis of 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff's base:
0.5g4-carbamoyl benzoate diamantane ester is dissolved in the dehydrated alcohol of 20mL, is slowly added drop-wise in the ethanol solution of the 10mL containing 0.19g near amino thiophenols; Dropwise, add 6-8 and drip analytical pure Glacial acetic acid, under nitrogen protection stirring at room temperature 5 hours; have a large amount of yellow mercury oxide to produce, leave standstill, cooling, filter, dehydrated alcohol recrystallization, dry; obtain pure yellow powder 4-carbamoyl benzoate diamantane ester contracting Ortho-Aminophenol Schiff's base, hydrogen spectrum is
1hNMR (500MHz, CDCl
3) δ 8.14 (d,
j=13.3Hz, 1H), 7.98 (d,
j=8.3Hz, 2H), 7.58 (d,
j=8.3Hz, 2H), 7.06 (d,
j=7.6Hz, 1H), 6.98 (dd,
j=11.1,4.2Hz, 1H), 6.79 (t,
j=7.5Hz, 1H), 6.71 (d,
j=7.8Hz, 1H), 6.42 (s, 1H), 2.25 (d,
j=12.9Hz, 9H), 1.78 – 1.67 (m, 6H), fusing point 220 DEG C ~ 223 DEG C;
(3) synthesis of nickel complex:
0.5g4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff's base is dissolved in 35mL dehydrated alcohol and N, in dinethylformamide mixed solvent, dehydrated alcohol and analytical pure N, dinethylformamide volume ratio is 6:1, under 65 DEG C of condition of heating and stirring, slowly to the 10mL ethanol solution containing 0.039g nickelous acetate in solution, reflux 3 hours, there is garnet to precipitate to generate, leave standstill, cooling, filter, dehydrated alcohol recrystallization, dry, obtain 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex dark red powder.
2. the application of 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex according to claim 1, is characterized in that 4-carbamoyl benzoate diamantane ester contracting near amino thiophenols Schiff base nickel complex can be applied in chemically modified electrode as electronic media.
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| CN106568818A (en) * | 2016-11-06 | 2017-04-19 | 桂林理工大学 | Nickel complex/graphene oxide modified glass-carbon electrode and manufacturing method thereof |
| CN107325021A (en) * | 2017-06-28 | 2017-11-07 | 哈尔滨理工大学 | O-aminophenol schiff bases and its synthetic method and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106568818A (en) * | 2016-11-06 | 2017-04-19 | 桂林理工大学 | Nickel complex/graphene oxide modified glass-carbon electrode and manufacturing method thereof |
| CN106568818B (en) * | 2016-11-06 | 2019-10-11 | 桂林理工大学 | A kind of nickel complex/graphene oxide modified glassy carbon electrode and preparation method thereof |
| CN107325021A (en) * | 2017-06-28 | 2017-11-07 | 哈尔滨理工大学 | O-aminophenol schiff bases and its synthetic method and application |
| CN107325021B (en) * | 2017-06-28 | 2019-04-26 | 哈尔滨理工大学 | O-aminophenol schiff bases and its synthetic method and application |
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